Method of producing partially cross-linked rubber-resin composition

Description

[0001] Various method are used for producing a partially cross-linked rubber-resin composition comprising a partially cross-linked peroxide-curable olefin copolymer rubber and a polyolefin resin. As the olefin copolymer rubber, ethylene/propylene copolymer rubber and ethylene/propylene/non-conjugated polyene copolymer rubber are typical.

[0002] One method disclosed in Japanese Unexamined Patent Publication No. 57-22036 (unpublished at the priority date of the present application) comprises melting and kneading the copolymer with an organic peroxide in a Banbury mixer to provide dynamic heat treatment for partial cross-linking, followed by mixing with a polyolefin resin. Another method disclosed in US-A-3806558 and US-A-4197381 comprises melting and kneading the copolymer rubber with an organic peroxide in a Banbury mixer in the presence of a peroxide-decomposing polyolefin resin such as polypropylene. Both of these are batchwise processes and so are not very economical methods of production. Further, in the former it is difficult to obtain a product of constant quality because of insufficient mixing of the partially cross-linked rubber and the polyolefin resin.

[0003] In order to obtain a homogeneous product of constant quality it is preferable to preliminarily melt and mix the copolymer rubber and a peroxide-decomposing polyolefin resin such as polypropylene and to form particles from the blend, and then to melt and knead the particles with an organic peroxide in an extruder for the dynamic heat treatment, for example, as described in US-A-4212787. This method incurs the disadvantages of requiring the preliminary step of melting and mixing the copolymer rubber and the polyolefin resin.

[0004] It would therefore be desirable to provide a continuous, single step, economic and advantageous method of producing a homogeneous partially cross-linked rubber-resin composition.

[0005] In the invention a partially cross-linked rubber-resin composition is made by melting and mixing a peroxide-curable olefin copolymer rubber and a peroxide-decomposing polyolefin resin with an organic peroxide compound, the rubber and the resin being subjected to dynamic heat treatment in the presence of the peroxide, and the method is characterised in that the rubber, in particulate form, the resin and the peroxide are fed to a twin screw extruder in which the dynamic heat treatment is carried out, under the condition:



wherein "x" stands for weight of the copolymer rubber (g/100 particle), and "y" stands for specific energy at the extrusion (kWhr/kg).

[0006] Thus, in the invention particulate rubber, resin and peroxide are fed directly to the twin screw extruder and it is possible by this method to produce a homogeneously mixed partially cross-linked copolymer rubber-resin composition having good properties. We find that the size of the rubber particles fed into the extruder significantly influences the properties of the final composition. Also the mechanical energy given by the twin screw extruder to the materials fed into it influences the dispersiblity of the partially cross-linked copolymer rubber and the polyolefin resin. The specific energy, which is correlated to the size of the copolymer rubber particles, preferably exceeds a certain level for the purpose of obtaining homogeneous mixing and optimum properties of the final product, as is described in more detail below.

[0007] We found that the use of a conventional single screw extruder was much less satisfactory. Although it is possible to choose the operating conditions of the single screw extruder so as to provide sufficient specific energy to the materials it is in practice almost impossible to achieve satisfactory dispersion of the partially cross-linked copolymer rubber and resin. As a result it is difficult or impossible to obtain, using a single screw extruder, the desired products having good properties.

[0008] The peroxide-curable olefin copolymer rubber to be partially cross-linked may be an essentially amorphous, elastic copolymer mainly composed of olefins, such as ethylene/propylene copolymer rubber, ethylene/propylene/non-conjugated diene terpolymer rubber, ethylene/butene copolymer, ethylene/1-butene/non-conjugated diene terpolymer rubber and ethylene/butadiene copolymer rubber. The elastic copolymer may be cross-linked when mixed with an organic peroxide and kneaded under heating to form a rubber of less or little fluidity. The copolymer rubber is made by copolymerizing ethylene and the alpha-olefin of 1 to 12 carbon atoms (e.g. propylene, butene-1, pentene-1, hexene-1, 4-methyl-1-pentene and 5-methyl-1-hexene) in a molar ratio of preferably about 50/50 to 95/5, more preferably, about 55/45 to 85/15. In cases when a non-conjugated polyene such as dicyclopentadiene, 1,4-hexadiene, cycloctadiene, vinyl norbornene, methylene norbornene or 5-ethylidene-2-norbornene is copolymerised, it is preferable that the amount of polyene is such that the iodine value is not more than about 50, preferably about 40 or less. Preferable the Mooney viscosity ML, ₁₄ (100°C) of the copolymer rubber is about 10 to 100, particularly about 40 to 150.

[0009] As the peroxide-decomposing polyolefin resin, the following resins may be used: crystalline polypropylene-based resins such as homopolymers of propylene and copolymers of at least 85 molar% propylene with' an alpha-olefin having 2 to 10 carbon atoms other than propylene, crystalline poly(1-butene)-based resins such as homopolymers of 1-butene, and copolymers of at least 85 molar% 1-butene with an alpha-olefin having 2 to 10 carbon atoms other than 1-butene and poly(4-methyl-1-pentene)-based resins such as homopolymers of 4-methyl-1-pentene, and copolymers at least 85 molar% 4-methyl-1-pentene with an alpha-olefin having 2 to 10 carbon atoms other than 4-methyl-1-pentene. The polypropylene-based resins and poly(1-butene)-based resins are preferable. Particularly, polypropylene-based resins having a melt index (230°C) of about 0.1 to 100, especially about 0.5 to 50 are very useful.

[0010] The peroxide-curable olefin copolymer rubber and the peroxide-decomposing polyolefin resin are mixed in a weight ratio of, generally about 10/90 to 95/5, preferably about 20/80 to 90/10. If the amount of the copolymer rubber is less than the above lower limit, excess decomposition of the resin component by the organic peroxide occurs and causes insufficient cross-linking of the copolymer rubber component as well as too much decrease in viscosity of the resin component, which results in poor dispersion between the partially cross-linked rubber and the resin. On the other hand, if the copolymer rubber is used in an amount higher than the above limit, the amount of resin component in the product is so low that strength of the product is unsatisfactory. Also, the resin component will have lower fluidity because the amount of the resin having decreased molecular weight is small, and therefore it is difficult to obtain a sufficient homogeneity in mixing, even if more of the resin component is added later to the dynamically heat treated materials with the intention to improve strength of the product.

[0011] Examples of the organic peroxide are: dicumyl peroxide, di-tert.-butyl peroxide, 2,5-dimethyl-2,5-di(tert.-butyl peroxy) hexane, 2,5-dimethyl-2,5-di-(tert.-butylperoxy)hexine-3, 1,3-bis(tert.-butyl peroxy isopropyl)benzene, 1,1-bis(tert.-butyiperoxy)-3,3,5-trimethy) cyclohexane, n-butyl-4,4-bis(tert.- butylperoxy)valerate, benzoyl peroxide, p-chlorbenzoyl peroxide, 2,4-dichlorbenzoyl peroxide, tert.-butyl peroxy benzoate, tert.-butyl peroxide isopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and tert.-butyl cumyl peroxide.

[0012] Out of these organic peroxides, preferable compounds in view of the anti-scorch stability and odour are 2,5-dimethyl-2,5-di(tert.-butyl peroxy)hexane, 2,5-dimethyl-2,5-di(tert.-butyl peroxy)hexine-3, 1,3- bis(tert.-butyl peroxy isopropyl)benzene, 1,1-bis-(tert.-butyl peroxy)-3,3,3-trimethyl cyclohexane, and n-butyl-4,4-bis(tert.-butyl peroxy)valerate. Among them 1,3-bis(tert.-butyl peroxy isopropyl)benzene is the best.

[0013] The organic peroxide is used in an amount of about 0.01 to 1 % by weight, preferably about 0.1 to 0.5% by weight, based on the total amount of the peroxide-curable olefin copolymer rubber, peroxide-decomposing polyolefin resin and optional components mentioned below.

[0014] The peroxide-curable olefin copolymer rubber is used in the form of particles. In this specification, the term "particle" means any particle form including pellet, granule, crumb and powder. Pellets are often preferred. The particles preferably have a maximum dimension (for instance a longer diameter) "z" not exceeding 25 mm, preferably 0.5 to 20 mm. This condition can be usually satisfied with the particle having a weight "x" not exceeding about 200 g/100 particles. It is preferable to use particulate copolymer rubber weighing about 50 g/100 particle or less. On the other hand, very small particles are difficult to produce and, even if commercially produced, expensive. So it is generally advisable to use particles weighing about 0.1 g/100 particle or more, preferably about 1 g/100-particle or more. The copolymer rubber particle of such size can be easily produced in accordance with the method, for example, described in U.S. Patent No. 3,586,089 using a pelletizer which performs removal of polymerization medium and pelletizing simultaneously.

[0015] The other component, the polyolefin resin should be also in the form of particles. Though the size of the resin particle may not be of the same fineness, it is generally preferable that the weight is in the range of about 1 to 10 g/100-particle.

[0016] The dynamic heat treatment according to the present invention is carried out under the condition of the specific energy fed to the twin screw extruder:

preferably, 1.5?y?0.003x+0.15, wherein the specific energy is defined as the quotient given by dividing the difference of the driving power of the extruder in which the dynamic heat treatment is performed (HP₁KW) and the driving power without load or no material feed under the same screw rotation (HP_ZKW) with the extruding amount (Q kg/hr). The unit thereof is KWhr/kg.

[0017] The specific energy may be varied by changing the operation conditions of the extruder. It may increase by increase in rotation of the screws, use of a finer screen pack, or decrease in feeding amount of the materials. Also, it depends on the type of the screws. Screws with shallower grooves will give increased specific energy.

[0018] Preferably the dynamic heat treatment gives the specific energy equal to or higher than the energy of the above equation, which energy is determined by the size of the rubber particle. A lower specific energy is unsatisfactory for the dispersion or thorough mixing, and gives the partially cross-linked rubber-resin composition having inferior properties. However, it is preferable that the specific energy does not exceed about 1.5 KWhr/kg, particularly about 1.0 KWhr/kg. If too much specific energy is given, local elevation of temperature will occur due to transfromation of mechanical energy to frictional energy, resulting in deterioration of properties of the product composition. Such an excess energy is of course neither necessary nor economical.

[0019] Various types of twin screw extruders which may give the above described specific energy may be used and the two screws may mutually engage or not. Examples of commercially available machines are Werner Extruder (made by Werner in West Germany, two screws engaging and rotating in the same direction). CIM-90 Extruder (made by Nippon Seiko, two screws not engaging and rotating in the different directions) and BT-80 Extruder (made by Hitachi, two screws engaging and rotating in the different directions).

[0020] The dynamic heat treatment using the twin screw extruder is carried out under the conditions of the temperature at which the materials melt, generally about 200 to 280°C, preferably about 210 to 250°C, and the residence time is, generally about 15 to 240 seconds, preferably about 30 to 180 seconds.

[0021] Homogeneous and moderate cross-linking reaction can be expected if a cross-linking-aid is present during the heat treatment. Such cross-linking aids are: sulphur, p-quinone dioxime, p,p'-dibenzoyl quinone dioxime, N-methyl-N,4-dinitrosoaniline, nitrobenzene, diphenyl guanidine, trimethylol propane-N,N'-m-phenylene dimaleimide, divinyl benzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, trimethylol propane trimethacrylate, allyl methacrylate, vinyl butylate, and vinyl stearate.

[0022] Out of the above compounds, divinyl benzene is the most preferable, because it is easy to handle and gives the composition having well-balanced properties. More particularly, divinyl benzene is liquid at a normal temperature and dissolves organic peroxide and has good compatibility with the peroxide-curable copolymer rubber and the polypropylene resin. It therefore is useful as a dispersing agent or diluent of the organic peroxide to improve dispersibility of the organic peroxide into the components of the composition, particularly into the peroxide-curable copolymer rubber component so as to cause homogeneous and moderate cross-linking thereof. Also, divinyl benzene itself provides a radical which acts as a chain transfer agent and cross-linking agent, and therefore, gives cross-linking effect higher than that given by sole use of an organic peroxide cross-linking agent. Further, divinyl benzene exhibits so good reactivity to the organic peroxide that very few portion remains in the produced partially cross-linked rubber-resin composition as the monomer, which may, if present, give odour to the product. Divinyl benzene may be used in the form of a mixture with some other materials such as hydrocarbons.

[0023] The above mentioned various cross-linking aids are used in an amount of up to 2 parts by weight, preferably about 0.3 to 1 parts, based on the total 100 parts by weight of the peroxide-curable copolymer rubber and the peroxide-decomposing polyolefin resin components. Too much addition of the cross-linking aid may, if a large amount of the organic peroxide is used, accelerate the cross-linking, and as the result, the partially cross-linked rubber-resin composition may have decreased homogeneity and low impact strength. On the other hand, if the amount of the organic peroxide is small, the cross-linking aid will remain in the partially cross-linked rubber-resin composition as unreacted monomer, which causes undesirable change in properties because of thermal effect during processing of the product.

[0024] For the purpose of improving further properties of the partially cross-linked rubber-resin composition, mineral oil softener, peroxide-non-curable hydrocarbon rubber and peroxide-curable polyolefin resin may be optionally added. Usual amount of addition is in the range of 0 to 400 parts by-weight, preferably 5 to 300 parts by weight, based on total 100 parts by weight of the rubber-resin composition. These additives can be added at the dynamic heat treatment. It is preferable to preliminarily add these additives to the rubber and/or resin. The mineral oil softeners are useful for improving processability of the partially cross-linked rubber-resin composition. The same effect can be obtained by addition of the peroxide-non-curable hydrocarbon rubber such as polyisobutylene, butyl rubber and propylene-ethylene copolymer rubber containing not higher than 50% ethylene unit. The peroxide-curable polyolefin resin such as polyethylene improves strength and impact resistance of the partially cross-linked rubber-resin composition.

[0025] As described above, it is possible to produce partially cross-linked rubber-resin compositions, which are homogeneously blended and have good properties, economically in single step by dynamic heat treatment in a twin screw extruder under specific conditions in accordance with the present invention. The obtained partially cross-linked rubber-resin compositions may be used as they are or as mixtures with further peroxide-curable or peroxide-decomposing polyolefin resin. Those compositions containing relatively large amount of the partially cross-linked rubber component are useful as thermoplastic elastomers, and those compositions containing relatively large amount of the polyolefin resin are useful as polyolefin resin composition having improved impact strength.

[0026] The present invention will be further illustrated by the following. examples.

Materials used

[0027] 

EPT-1: 100 parts by weight of ethylene/propylene/dicyclopentadiene terpolymer rubber [molar ratio of ethylene/propyiene:78122, ML, ₁₄ (100°C):160, iodine value:13L to which 40 parts by weight of mineral oil softener [PW-100, made by Idemitsu Petrochemical] is added.

EPT-2: ethylene/propylene/ethylidene norbornene terpolymer rubber [molar ratio of ethylene/ propylene:79/21, ML,,₄ (100°C):100, iodine value:15]

PP-1: crystalline polypropylene having melt index (230°C) of 12 (weight of the particle:3 g/100- particle)

PP-2: crystalline polypropylene containing a small quantity of copolymerised ethylene having melt index (230°C) of 30 (weight of the particle:3 g/100-particle)

PER: propylene/ethylene copolymer rubber [molar ratio of propylene/ethylene: 70/30, [η] (135°C, decaline):3.0 dl/g, weight of the particle:3 g/100-particle]

[0028] Organic Peroxide: 1,3-bis(tert.-butyl peroxyisopropyl) benzene

Procedures

[0029] Particles of EPT-1, PP-1 or PP-2, and PER and/or mineral oil softener for the low hardness series, were preliminarily blended in a Henshel Mixer for 60 seconds, and the blends of certain amounts were fed to various extruders through constant feeders. Samples were taken by strand-cutting at dies of the extruders.

[0030] In the Controls (shown in Tables I and II), conventional single screw extruder of dia.-90 mm (P-90, made by Nippon Seiko) was used, with which two kinds of screws, i.e. a full freight screw for pelletizing and an end-damaged screw having a seal ring for resin-blending (UD=28 in both the screws) were tested. Detailed operation conditions were as follows:

[0031] In some examples and the Controls for comparison therewith (shown in Tables III through VII), twin screw extruder (W & P, made by Werner, diameter 90 mm, UD=43) was used. The specific energy was varied by changing the screw rotation and the extrusion rate. Detailed operation conditions were as follows:

[0032] In the other examples and the Controls for comparison therewith (shown in Tables VIII and IX), a twin screw extruder (made by Hitachi, diameter 80 mm, L/D=16) was used. The specific energy was varied by changing the screw rotation and the extrusion rate. Detailed operation conditions were as follows:

Evaluation

1. Homogeneity:

[0033] The extruded particles were press-formed at 200°C to form thin sheets of thickness 0.2 to 0.4 mm, and the surfaces thereof were inspected.

(Grades) A: quite homogeneous

B: a certain extent of abnormality

C: serious abnormality

2. Processability:

1) Processability at Injection Moulding

[0034] 

Machine: Dynamelter (made by Meiki Manufacturing)

Temperature: 200°C

Pressure of Injection: primary 1300 kg/cm²
secondary 700 kg/c_m²

Injecting Pressure: maximum

Processing speed: 90 seconds/cycle

Mould: square plates type with two point gates

Product: three types of square plates (length: 300 mm, width: 180 mm, and thickness: 2, 4 and 7 mm) The surfaces of the product plates were inspected as done for the above sheets.

2) Processability at Extrusion Moulding

[0035] 

Machine: 40 mm-diameter extruder (made by Toshiba Machinery)

Temperature: 210°C

Die: straight die (die/core=12.₅ mm/10.0 mm)

Drawing Speed: 10 m/min.

Product: tube

[0036] The surfaces of the product tubes thus obtained were inspected as done for the above sheets.

3. Basic Properties

[0037] The above injection-moulded square plates (thickness 2 mm) were subjected to measurement of stress at 100% elongation, stress and elongation at breaking, surface hardness and permanent strain (at 100% elongation) in accordance with the testing method defined by JIS K-6301.

[0038] Notes on the Results shown in Tables I through XI.

Table I:

[0039] A single-screw extruder was used, and the specific energy was varied in the range from 0.12 to 0.45 by changing rotation of screw and feeding rate. The obtained products of high hardness series were not satisfactory because of insufficient homogeneity and some other properties. The extruder used in this Table (and in Table II) was either Type 1 or Type 2. Type 1 is a full freight extruder and Type 2 was end-damaged with seal ring.

Table II:

[0040] Another single-screw extruder was used, and the specific energy was varied in the range from 0.11 to 0.41 by changing rotation of screw and feeding rate. The obtained products of low hardness series were also not satisfactory because of insufficient homogeneity and some other properties.

Table III to VII:

[0041] The twin screw extruder made by Werner was used, and the specific energy was varied by changing rotation of screw and extrusion rate. From the experimental data, it was found that the factors giving satisfactory products are as follows:

[0042] Thus, it was concluded that the specific energy "y" should be such a value as determined by the weight of the copolymer rubber particle "x" according to the equation below:

[0043] 

preferably

[0044] 

Table VIII to IX:

[0045] A twin screw extruder made by Hitachi was used, and the specific energy was varied by changing rotation of screw and extrusion rate. The data showed that the factors giving satisfactory products are as follows:

Table X:

[0046] A twin screw extruder made by Hitachi was used to prepare the Low Hardness Series-2. The specific energy was varied by changing rotation of screw and extrusion rate.

[0047] The following conversion factors may be used to convert the units used in this specification (including the Tables) to S1 units:-

Claims

1. A method of producing a partially cross-linked rubber-resin composition by melting and mixing a peroxide-curable olefin copolymer rubber and a peroxide-decomposing polyolefin resin with an organic peroxide compound in which method the rubber and the resin are mixed in a weight ratio in the range 10:90 to 95:5 and are subjected to dynamic heat treatment in the presence of the peroxide characterised in that the rubber in particulate form and the resin and peroxide are fed to a twin screw extruder in which the dynamic heat treatment is carried out, under the condition:



wherein "x" stands for weight of the copolymer rubber (g/100 particle), and "y" stands for specific energy at the extrusion (KWhr/kg).

2. A method according to claim 1 characterised in that the rubber particles have a maximum dimension not exceeding 25 mm.

3. A method according to claim 2 characterised in that the rubber particles have a maximum dimension of from 0.5 to 20 mm.

4. A method according to claim 3 characterised in that x is 1 to 50.

5. A method according to claim 3 or claim 4 characterised in that y is 1.5 or less.

6. A method according to any preceding claim characterised in that the polyolefin resin is fed into the extruder in the form of particles having a weight in the range of 1 to 10 g/100 particles.

7. A method according to any preceding claim characterised in that the weight ratio of rubber:resin is 20:80 to 90:10.

8. A method according to any preceding claim characterised in that a cross-linking aid, preferably divinylbenzene, is present during the heat treatment.

9. A method according to any preceding claim characterised in that the rubber is an amorphous copolymer of olefins, or an amorphous copolymer of olefins and non-conjugated diene and the resin is a crystalline polypropylene, poly(1-butene) or poly(4-methyl-1-pentene) or a copolymer containing at least 85 molar% thereof with an alpha olefin containing 2 to 10 carbon atoms.

Ansprüche

1. Verfahren zur Herstellung einer teilweise vernetzten Kautschuk-Harz-Zusammensetzung durch Schmelzen und Mischen eines Peroxid-härtbaren Olefincopolymer-Kautschuks und eines Peroxidzersetzenden Polyolefinharzes mit einer organischen Peroxidverbindung, wobei bei dem Verfahren der Kautschuk und das Harz in einem Gewichtsverhältnis im Bereich von 10:90 bis 95:5 gemischt werden und einer dynamischen Wärmebehandlung in Anwesenheit des Peroxids unterworfen werden, dadurch gekennzeichnet, daß der teilchenförmige Kautschuk und das Harz und Peroxid in eine Doppel schnecken-Strangpresse gegeben werden, in welcher die dynamische Wärmebehandlung durchgeführt wird, und zwar unter der Bedingung:



worin "x" das Gewicht des Copolymer-Kautschuks (g/100 Teilchen) darstellt und "y" die spezifische Energie beim Strangpressen (kWhr/kg) ist.

2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Kautschukteilchen eine maximale Dimension von nicht mehr als 25 mm haben.

3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß die Kautschukteilchen eine maximale Dimension von 0,5 bis 20 mm haben.

4. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß x=1 bis 50 ist.

5. Verfahren nach Anspruch 3 oder 4, dadurch gekennzeichnet, daß y=1.5 oder weniger ist.

6. Verfahren nach einem der vorausgehenden Ansprüche, dadurch gekennzeichnet, daß das Polyolefin-Harz in die Strangpresse in Teilchenform mit einem Gewicht im Bereich von 1-10 g/100 Teilchen gegeben wird.

7. Verfahren nach einem der vorausgehenden Ansprüche, dadurch gekennzeichnet, daß das Gewichtsverhältnis Kautschuk:Harz=20:80 bis 90:10 ist.

8. Verfahren nach einem der vorausgehenden Ansprüche, dadurch gekennzeichnet, daß ein Vernetzungs-Hilfsmittel, vorzugsweise Divinylbenzol, während der Wärmebehandlung anwesend ist.

9. Verfahren nach einem der vorausgehenden Ansprüche, dadurch gekennzeichnet, daß der Kautschuk ein amorphes Olefincopolymer oder ein amorphes Copolymer von Olefinen und einem nicht-konjugierten Dien ist und das Harz ein kristallines Polypropylen, Poly(1-buten) oder Poly(4-methyl-1-penten) oder ein zumindest 85 Mol-% davon enthaltendes Copolymer mit einem a-Olefin mit 2-10 Kohlenstoffatomen ist.

Revendications

1. Méthode de production d'une composition de résine-caoutchouc partiellement réticulé par fusion et mélangeage d'un caoutchouc de copolymère d'oléfine durcissable par un peroxyde et d'une résine de polyoléfine décomposant le peroxyde, avec un composé peroxyde organique, méthode dans laquelle de caoutchouc et la résine sont mélangés dans un rapport pondéral dans l'intervalle de 10:90 à 95:5 et sont soumis à un traitement thermique dynamique en présence de peroxyde, ladite méthode étant caractérisée en ce que le caoutchouc sous forme de particules et la résine et le peroxyde sont alimentés dans une extrudeuse à double vis dans laquelle le traitement thermique dynamique est conduit, dans les conditions suivantes:



où "x" désigne le poids du caoutchouc de copolymère (g/100 particules), et "y" désigne l'énergie spécifique à l'extrusion (kWh/kg).

2. Méthode selon la revendication 1, caractérisée en ce que les particules de caoutchouc ont une dimension maximale ne dépassant pas 25 mm.

3. Méthode selon la revendication 2, caractérisée en ce que les particules de caoutchouc ont une dimension maximale de 0,5 à 20 mm.

4. Méthode selon la revendication 3, caractérisée en ce que x est égal à 1 à 50.

5. Méthode selon la revendication 3 ou 4, caractérisée en ce que y est égal à 1.5 ou moins.

6. Méthode selon l'une quelconque des revendications précédentes, caractérisée en ce que la résine de polyoléfine est alimentée dans l'extrudeuse sous la forme de particules ayant un poids dans l'intervalle de 1 à 10 g/100 particules.

7. Méthode selon l'une quelconque des revendications précédentes, caractérisée en ce que le rapport pondéral caoutchouc:résine est de 20:80 à 90:10.

8. Méthode selon l'une quelconque des revendications précédentes, caractérisée en ce qu'un adjuvant de réticulation, de préférence le divinylbenzène, est présent durant le traitement thermique.

9. Méthode selon l'une quelconque des revendications précédentes, -caractérisée en ce que le caoutchouc est un copolymère amorphe d'oléfine, ou un copolymère amorphe d'oléfine et de diène non conjugué et la résine est un polypropylène cristallin, un poly(1-butène) ou un poly(4-méthyl-1-pentène) ou un copolymère contenant au moins 85% molaires de ceci avec une a-oléfine contenant de 2 à 10 atomes de carbone.